CN104764780A - Battery for in-situ spectral analysis and use method and application thereof - Google Patents
Battery for in-situ spectral analysis and use method and application thereof Download PDFInfo
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Abstract
The invention relates to the field of batteries, in particular to a battery for in-situ spectral analysis and a use method and application thereof, wherein the battery comprises a top cover, a sealing sleeve, a shell lining pipe, a conductive compression column, a conductive spring, a conductive pressing sheet, a working electrode pole and a reference electrode pole, and the assembly steps are as follows: inserting the inner liner tube of the shell into the bottom of the shell; sequentially placing a working electrode, a battery diaphragm and a reference electrode into the lining tube, so that the working electrode is positioned on the opposite side of an observation window at the bottom of the shell; sequentially placing the conductive pressing sheet, the conductive spring and the conductive pressing column into the lining tube, and pressing the conductive pressing sheet on the reference electrode; the outer side of the shell is connected with the inner side of the sealing sleeve, and the outer side of the sealing sleeve is connected with the inner side of the top cover through threads; screwing all the threaded connecting pieces to complete the sealing of the battery; the working electrode pole and the reference electrode pole are respectively connected with the shell and the top cover through threads. By means of the invention, various in-situ spectroscopic studies can be conveniently carried out on the surface of the electrode in the charging and discharging processes.
Description
Technical Field
The invention relates to the field of batteries, in particular to a battery for in-situ spectral analysis.
Background
With the continuous improvement of the energy demand of modern industry, advanced electrochemical energy storage devices represented by lithium ion batteries, lithium-sulfur batteries and sodium ion batteries become key core technologies in the fields of digital electronics, electric automobiles, smart power grids and the like due to the obvious advantages of the advanced electrochemical energy storage devices in terms of energy density and economic cost. Although these electrochemical energy storage systems have shown good promise in primary applications, current research is still in the initiative for the electrochemical reaction processes of these batteries. In order to understand the electrochemical reaction process of the battery deeply, understand the charge and discharge reaction mechanism of the battery, reveal various dynamic and thermodynamic factors influencing the electrode process, the in-situ analysis needs to be carried out during the charge and discharge process of the battery. The in-situ spectroscopic analysis methods including in-situ Raman spectroscopy, in-situ infrared spectroscopy, in-situ ultraviolet-visible spectroscopy, in-situ X-ray diffraction spectroscopy, in-situ X-ray photoelectron spectroscopy and the like can represent the element, structure and phase change of the electrode material in the battery charging and discharging process in real time, avoid the deviation of static and quasi-static measurement on the experimental result, and provide reliable theoretical and experimental basis for the research of the electrochemical reaction process. However, in-situ spectroscopy research on the electrochemical reaction process of the battery requires a battery device with a special structure, and most of the existing patent technologies have the defects of complex device structure, high manufacturing cost and the like, thereby forming a barrier to the application and popularization of the battery device. Meanwhile, most of the prior art patents are in-situ battery devices used for certain types of spectrum analysis (such as X-ray diffraction spectrum), and these devices are generally not suitable for other types of in-situ spectrum analysis and detection, and thus lack versatility.
Although the battery devices disclosed in chinese patents (CN 100373168C, CN102435625A, CN 203434214U) can perform in-situ X-ray diffraction spectrum measurement, the electrode portion is not provided with a pressing device, so that there is a defect in pressing tightness, which may further affect the electrical contact between the electrode material and the surface of the current collector during the charging and discharging processes, and is not favorable for the long-term stable cycle of the battery. Chinese patent CN104393223A discloses an in-situ battery accessory of an X-ray diffractometer, which can perform in-situ X-ray diffraction spectrum characterization on a lithium ion battery, and in order to enhance the sealing performance of the battery, the device adopts a plurality of sealing rings for sealing, but this also increases the complexity of the device structure and the battery assembly process, and is not beneficial to the practical application thereof. Chinese patent No. 103399000A discloses an electrolytic cell device for raman spectroscopy in-situ characterization, in which working and reference electrodes are extended out of the electrode device, so that the device can only be used in conjunction with a specific model of raman spectroscopy, and the number of components is excessive, thereby increasing the complexity of the structure and the assembly process. Finally, the battery devices can only be used for single-type spectroscopy detection and analysis, and are lack of universality. Therefore, the invention provides the general in-situ spectral analysis cell device with simple structure and assembly, low cost and good sealing performance, and has important significance.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a cell for in-situ spectral analysis, which has the advantages of simple structure, low cost, good sealing property and strong universality and is used for various in-situ spectral detections in the charging and discharging processes of the cell.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention relates to a cell for in-situ spectral analysis, which is characterized in that: the battery is characterized in that a shell inner lining pipe is arranged in a shell, a conductive compaction structure is arranged in the shell inner lining pipe, a top cover is arranged on the shell, and the shell and the top cover are sealed through a sealing sleeve;
a working electrode pole and a reference electrode pole are respectively fixed on the shell and the top cover;
the bottom end of the shell is provided with a through hole, a transparent sealing material covers the through hole and the outer side of the shell, and the through hole and the transparent sealing material form an observation window; the diameter of the through hole is 0.5-5 mm, and preferably 1-3 mm; the transparent sealing material can be selected from an ultrathin quartz sheet, an ultrathin corundum sheet, an ultrathin glass sheet, an ultrathin beryllium sheet, ITO conductive glass or a polyimide film; the transparent sealing material may be in any shape, but is preferably square or circular, has a size sufficient to cover the through-hole, and has a thickness of 50 to 2000 μm, and preferably 100 to 500 μm.
The conductive pressing structure is formed by sequentially sleeving a conductive pressing sheet, a conductive spring and a conductive pressing column.
The cell for in-situ spectral analysis of the invention is also characterized in that: a cylindrical groove is formed in the bottom of the conductive pressing column, a cylindrical boss is arranged at the top of the conductive pressing sheet, and the height of the cylindrical boss is not larger than the depth of the cylindrical groove; the length of the conductive spring is greater than the depth of the cylindrical groove, the outer diameter of the conductive spring is smaller than the inner diameter of the cylindrical groove, and the inner diameter of the conductive spring is greater than the outer diameter of the cylindrical boss; the conductive pressing plate, the conductive spring and the conductive pressing column are sequentially sleeved to form the conductive pressing structure.
The sealing sleeve and the inner liner of the shell are made of insulating materials; the insulating material is a high polymer material. The high polymer material can be selected from one of polytetrafluoroethylene, phenolic resin, epoxy resin, polyformaldehyde, polyethylene, polyvinyl chloride, polypropylene, polyether ether ketone, polysulfone, polyimide, polyvinylidene fluoride, polyethylene terephthalate, polyphenyl ether, polyphenylene sulfide, chlorinated polyvinyl chloride, polyacrylonitrile, polybutylene terephthalate, polycarbonate, polyamide imide, polyurethane and poly-p-phenylene terephthalamide or a combination thereof, and preferably one of polytetrafluoroethylene, phenolic resin, epoxy resin, polyacrylonitrile and polyimide or a combination thereof.
The top cover, the shell, the conductive pressing column, the conductive spring, the conductive pressing sheet, the working electrode pole and the reference electrode pole are made of conductive materials. The conductive material may be selected from metal materials such as stainless steel, iron, copper, aluminum, titanium, nickel, etc., or alloys formed of these metal materials, and preferably stainless steel, titanium, nickel.
The top cover, the sealing sleeve and the shell are matched through threads. The inside of the cap, the inside and outside of the sealing sleeve, and the outside of the housing are provided with threads so as to be connected to each other by means of a threaded engagement.
The inner diameter of the top cover is equal to the outer diameter of the sealing sleeve, the inner diameter of the sealing sleeve is equal to the outer diameter of the shell, the inner diameter of the shell is equal to the outer diameter of the lining pipe in the shell, and the inner diameter of the lining pipe in the shell is equal to the outer diameter of the conductive compression column.
The top cover and the shell are respectively provided with a threaded hole for fixing the reference electrode pole and the working electrode pole through threaded fit.
Another object of the present invention is to provide a method for using the above cell for in situ spectroscopic analysis, the method comprising the steps of:
a. inserting the liner tube in the shell to the bottom of the shell;
b. sequentially placing the working electrode and the battery diaphragm into the lining tube of the shell, and enabling the working electrode to be opposite to the through hole;
c. covering a transparent sealing material on the through hole from the outer side of the shell, and tightly adhering the periphery of the sealing material with the outer surface of the shell by using a sealing agent to form an observation window;
d. injecting electrolyte into the lining tube in the shell, wherein the addition amount of the electrolyte is determined according to the inner diameter of the lining tube in the shell and the thickness of the battery diaphragm, so that the electrolyte can fully infiltrate the diaphragm and wet the surface of the working electrode;
e. putting the reference electrode into a lining tube of the shell, covering the reference electrode on a battery diaphragm, and enabling the electrolyte to wet the surface of the reference electrode;
f. sequentially placing the conductive pressing sheet, the conductive spring and the conductive pressing column into the lining tube of the shell to form a conductive pressing mechanism, and pressing the conductive pressing sheet on the reference electrode;
g. connecting the outer side of the shell with the inner side of the sealing sleeve through threads, and screwing and sealing;
h. connecting the outer side of the sealing sleeve with the inner side of the top cover through threads, and screwing and sealing;
i. connecting the working electrode pole and the reference electrode pole with threaded holes in the shell and the top cover respectively through threads;
j. placing the connected battery on a sample table of a spectroscopic characterization instrument, aligning a light source to a through hole on an observation window, and adjusting the focal length of the light source to enable light rays to pass through the observation window and be focused on the surface of a working electrode;
k. and respectively connecting the working electrode pole and the reference electrode pole with corresponding electrode leads of an electrochemical testing device, and acquiring electrochemical and spectral signals after setting relevant parameters.
The outer diameters of the working electrode, diaphragm and reference electrode are preferably the same as the inner diameter of the liner within the housing.
The working electrode and the reference electrode may be selected from a positive electrode or a negative electrode of a secondary battery system such as a lead-acid battery, a nickel-cadmium battery, a nickel-hydrogen battery, an all-vanadium redox flow battery, a metallic lithium secondary battery (e.g., a lithium-air battery, a lithium-sulfur battery, a lithium-selenium battery, etc.), a lithium ion battery, a sodium ion battery, a metallic sodium secondary battery (e.g., a sodium-sulfur battery, a sodium-selenium battery, etc.), a magnesium ion battery, a metallic magnesium secondary battery (e.g., a magnesium-sulfur battery, etc.), a metallic zinc secondary battery, a secondary zinc-manganese battery, etc., and a positive electrode or a negative electrode of a primary battery system such as a zinc-air battery, an alkaline zinc-manganese battery, a zinc-silver battery, a lithium-manganese battery, etc.
The battery diaphragm can be a polymer microporous diaphragm, such as a polyethylene microporous diaphragm, a polypropylene microporous diaphragm, a polyimide microporous diaphragm, or a composite thereof (such as a polypropylene/polyethylene microporous diaphragm), and can also be a non-woven fabric diaphragm, such as a glass fiber non-woven fabric diaphragm, a synthetic fiber non-woven fabric diaphragm, a ceramic fiber paper diaphragm, or a composite diaphragm thereof; the battery diaphragm is preferably a polyethylene microporous diaphragm, a polypropylene/polyethylene microporous diaphragm and a glass fiber non-woven fabric diaphragm.
The sealant can be selected from vacuum silicone grease, vaseline or sealant, preferably vacuum silicone grease.
The choice of the transparent encapsulant is determined by the spectroscopic characterization instrument used.
The electrolyte can be selected from lead-acid batteries, nickel-cadmium batteries, nickel-hydrogen batteries, all-vanadium redox flow batteries, metal lithium secondary batteries (such as lithium-air batteries, lithium-sulfur batteries, lithium-selenium batteries and the like), lithium ion batteries, sodium ion batteries, metal sodium secondary batteries (such as sodium-sulfur batteries, sodium-selenium batteries and the like), magnesium ion batteries, metal magnesium secondary batteries (such as magnesium-sulfur batteries and the like), metal zinc secondary batteries, secondary zinc-manganese batteries and other secondary battery systems, and common electrolytes of zinc-air batteries, alkaline zinc-manganese batteries, zinc-silver batteries, lithium-manganese batteries and other primary battery systems.
The addition amount V 'of the electrolyte is determined according to the volume V of the battery separator in the casing lining tube, and preferably V' =0.5 to 2V.
The spectroscopic characterization instrument may be selected from a raman spectrometer, an infrared spectrometer, an ultraviolet-visible spectrometer, a fluorescence spectrometer, an X-ray diffraction spectrometer or an X-ray photoelectron spectrometer.
The electrochemical testing device can be selected from an electrochemical workstation, a potentiostat or a battery charge and discharge testing system.
It is a further object of the present invention to provide a use of a cell for in situ spectroscopy, characterized in that: the in-situ spectroscopic analysis comprises in-situ Raman spectroscopic analysis, in-situ infrared spectroscopic analysis, in-situ ultraviolet-visible spectroscopic analysis, in-situ fluorescence spectroscopic analysis, in-situ X-ray diffraction spectroscopic analysis, and in-situ X-ray photoelectron spectroscopic analysis.
Compared with the prior art, the cell for in-situ spectral analysis provided by the invention has the following beneficial effects:
1. simple structure and assembly, low cost: compared with the prior art, the battery for in-situ spectral analysis has fewer components, the cost of key components is low, and the battery is convenient to produce and process; the battery parts are mainly connected by threads during assembly, the assembly process is simple, and the technical popularization and application are convenient;
2. the sealing performance is excellent, and the stability is good: compared with the prior art, the battery for in-situ spectral analysis skillfully utilizes the sealing sleeve pipe with internal and external threads to realize the one-time integral sealing of the shell and the top cover, and has simple operation and excellent sealing performance; the battery is provided with a conductive pressing mechanism, so that the electrode material can be kept in close contact with the surface of a current collector in the charging and discharging processes, and the stability of subsequent in-situ electrochemical tests and spectroscopy characterization can be guaranteed;
3. the universality is strong: compared with the prior art, the battery for in-situ spectral analysis is not limited to a certain spectroscopy test technology, and can be matched with different spectroscopy instruments to carry out various in-situ spectroscopy tests by simply replacing the transparent sealing material of the observation window. By means of the advantage of strong universality of the battery, various in-situ spectroscopic analysis researches can be conveniently carried out on the element composition, the structure and the phase change of the electrode active material in the electrochemical reaction process, and reliable theoretical and experimental bases are provided for the understanding of the charging and discharging mechanism of the battery, the disclosure of various dynamic and thermodynamic factors influencing the electrode process.
Drawings
FIG. 1 is a perspective view of a cell for in situ spectroscopic analysis in accordance with the present invention;
FIG. 2 is a perspective view of a cell for in situ spectroscopy according to the present invention in another orientation;
FIG. 3 is a top view of a cell for in situ spectroscopic analysis in accordance with the present invention;
FIG. 4 is a side view of a cell for in situ spectroscopic analysis in accordance with the present invention;
FIG. 5 isbase:Sub>A cross-sectional view taken along the line A-A in FIG. 4;
FIG. 6 is a schematic diagram of the working state of the in-situ spectroscopic analysis cell of the present invention after the working electrode, the cell diaphragm, the reference electrode and the electrolyte are added, wherein the right-side small diagram is a partial enlarged view of the connecting portion of the cell diaphragm with the working electrode and the reference electrode;
the labels in the figure are: 1, top cover; 2, sealing the sleeve; 3, a shell; 4, lining a pipe in the shell; 5, conducting a compression column; 5a cylindrical groove; 6 a conductive spring; 7, conducting tabletting; 7a cylindrical boss; 8 working electrode pole column; 9 reference electrode post; 10 through holes; 11 a transparent sealing material; 12 working electrode, 13 battery diaphragm, 14 reference electrode; 15 electrolyte solution.
Detailed Description
The technical solution of the present invention is further described below with reference to the following embodiments and the accompanying drawings.
Example 1
Referring to fig. 1 to 5, the present embodiment provides a cell for in-situ spectroscopic analysis, which includes a top cover 1, a sealing sleeve 2, a housing 3, a liner tube 4 inside the housing, a conductive compression column 5, a conductive spring 6, a conductive compression sheet 7, a working electrode post 8, and a reference electrode post 9.
The bottom of the shell 3 is provided with a through hole 10 with the diameter of 1mm, the part of the through hole 10 at the outer side of the shell 3 is bonded with a square ultrathin quartz plate with the side length of 3mm and the thickness of 200 mu m by vacuum silicone grease to be used as a transparent sealing material 11, and the square ultrathin quartz plate and the through hole 10 form an observation window together.
The material of the sealing sleeve 2 and the material of the liner tube 4 in the shell are both polytetrafluoroethylene, and the material of other components is stainless steel.
The internal diameter of the top cover 1 and the external diameter of the sealing sleeve 2 are both 24mm, the internal diameter of the sealing sleeve 2 and the external diameter of the shell 3 are both 20mm, the internal diameter of the shell 3 and the external diameter of the shell internal liner tube 4 are both 16mm, and the internal diameter of the shell internal liner tube 4 and the external diameter of the conductive compression column 5 are both 12mm.
The inside of the cap 1, the inside and outside of the sealing sleeve 2, and the outside of the housing 3 are provided with threads so as to be connected to each other by means of a threaded engagement.
The conductive compression column 5 is provided with a cylindrical groove 5a with the depth of 6mm and the inner diameter of 6mm; the length of the conductive spring 6 is 7mm, the outer diameter is 5.5mm, and the inner diameter is 5mm; the conductive pressing sheet 7 is provided with a cylindrical boss 7a with the length of 6mm and the diameter of 4mm, and after the conductive spring 6 is placed into the cylindrical groove 5a, the conductive spring and the cylindrical boss 7a of the conductive pressing sheet 7 can be sleeved to form a conductive pressing mechanism.
The top cover 1 and the shell 3 are respectively provided with a threaded hole which can be connected with the reference electrode post 9 and the working electrode post 8 in a threaded joint mode.
As shown in fig. 6, using the above battery device, with an elemental sulfur positive electrode as a working electrode 12, a glass fiber non-woven fabric diaphragm as a battery diaphragm 13, a metal lithium negative electrode as a reference electrode 14, and a lithium-sulfur battery electrolyte as an electrolyte 15, a lithium-sulfur battery is assembled, and the steps of performing in-situ raman spectroscopy on the working electrode are as follows:
a. inserting the inner liner 4 of the shell into the bottom of the shell 3;
b. and sequentially placing the elemental sulfur anode and the glass fiber non-woven fabric diaphragm into the liner tube 4 in the shell, so that the elemental sulfur anode is opposite to the through hole 10, the diameters of the elemental sulfur anode and the glass fiber non-woven fabric diaphragm are both 12mm, and the thickness of the diaphragm is 0.5mm.
c. Covering the other side of the through hole 10 with an ultrathin quartz plate as a transparent sealing material 11, and tightly bonding the periphery of the ultrathin quartz plate with the outer surface of the bottom of the shell 3 by using vacuum silicone grease to form an observation window;
d. injecting lithium-sulfur battery electrolyte into the liner tube 4 in the shell, wherein the diameter of the glass fiber non-woven fabric diaphragm is 12mm and the thickness of the glass fiber non-woven fabric diaphragm is 0.5mm, so that the volume of the battery diaphragm is V = pi x (12 mm/2) 2 *0.5mm =56.5 μ L, and the preferable adding amount of the electrolyte 15 is V' =1.0 × V =56.5 μ L, so that the electrolyte can fully infiltrate the battery diaphragm 13 and wet the surface of the elemental sulfur anode;
e. the lithium metal negative electrode, in this example 12mm in diameter, is placed in liner tube 4 within the can, covering battery separator 13, and electrolyte 15 is allowed to wet the surface of the lithium metal negative electrode.
f. Sequentially placing a conductive pressing sheet 7, a conductive spring 6 and a conductive pressing column 5 into the lining tube 4 to form a conductive pressing mechanism, and pressing the conductive pressing sheet 7 on the metal lithium cathode;
g. connecting the outer side of the shell 3 with the inner side of the sealing sleeve 2 through threads, and screwing and sealing;
h. connecting the outer side of the sealing sleeve 2 with the inner side of the top cover 1 through threads, and screwing and sealing;
i. respectively connecting a working electrode post 8 and a reference electrode post 9 with threaded holes on the shell 3 and the top cover 1 through threads;
j. the connected battery is horizontally placed on a sample table of a Raman spectrometer, a light source is aligned to a through hole in an observation window, and light rays pass through the observation window and are focused on the surface of a working electrode by adjusting the focal length of the light source;
k. and respectively connecting the working electrode post 8 and the reference electrode post 9 with corresponding electrode leads of an electrochemical testing device, and acquiring electrochemical and in-situ Raman spectrum signals after setting relevant parameters.
Example 2
Referring to fig. 1 to 5, the present embodiment provides a cell for in-situ spectroscopic analysis, which includes a top cover 1, a sealing sleeve 2, a housing 3, a liner tube 4 inside the housing, a conductive compression column 5, a conductive spring 6, a conductive compression sheet 7, a working electrode post 8, and a reference electrode post 9.
The bottom of the shell 3 is provided with a through hole 10 with the diameter of 2mm, the part of the through hole 10 at the outer side of the shell 3 is bonded with a round ultrathin corundum piece 11 with the diameter of 5mm and the thickness of 100 mu m by vaseline, and the round ultrathin corundum piece 11 and the through hole 10 form an observation window together.
The sealing sleeve 2 and the lining pipe 4 in the shell are made of phenolic resin, and the rest components are made of titanium.
The internal diameter of the top cover 1 and the external diameter of the sealing sleeve 2 are both 20mm, the internal diameter of the sealing sleeve 2 and the external diameter of the shell 3 are both 17mm, the internal diameter of the shell 3 and the external diameter of the liner tube 4 in the shell are both 15mm, and the internal diameter of the liner tube 4 in the shell and the external diameter of the conductive compression column 5 are both 10mm.
The inside of the cap 1, the inside and outside of the sealing sleeve 2, and the outside of the housing 3 are provided with threads so as to be connected to each other by means of a threaded engagement.
The conductive compression column 5 is provided with a cylindrical groove 5a with the depth of 10mm and the inner diameter of 5mm; the length of the conductive spring 6 is 13mm, the outer diameter is 4mm, and the inner diameter is 3.2mm; the conductive pressing sheet 7 is provided with a cylindrical boss 7a with the length of 8mm and the diameter of 3mm, and after the conductive spring 6 is placed into the cylindrical groove 5a, the conductive spring and the cylindrical boss 7a of the conductive pressing sheet 7 can be sleeved to form a conductive pressing mechanism.
The top cover 1 and the shell 3 are respectively provided with a threaded hole which can be used for connecting a reference electrode pole 9 and a working electrode pole 8 in a threaded joint mode.
As shown in fig. 6, with the above battery device, a porous carbon electrode of a sodium ion battery is used as a working electrode 12, a polyethylene/polypropylene microporous membrane is used as a battery membrane 13, a metal sodium cathode is used as a reference electrode 14, an electrolyte of the sodium ion battery is used as an electrolyte 15, a half battery is assembled, and the step of performing in-situ infrared spectroscopy analysis on the working electrode is as follows:
a. inserting the inner liner 4 of the shell into the bottom of the shell 3;
b. sequentially placing a porous carbon electrode and a polyethylene/polypropylene microporous diaphragm into the liner tube 4 in the shell to enable the porous carbon electrode to be opposite to the through hole 10; the diameters of the porous carbon electrode and the polyethylene/polypropylene microporous diaphragm are both 10mm, and the thickness of the diaphragm is 0.2mm.
c. Covering the other side of the through hole 10 with a round ultrathin corundum sheet as a transparent sealing material 11, and tightly bonding the periphery of the round ultrathin corundum sheet with the outer surface of the bottom of the shell 3 by using vaseline to form an observation window;
d. the electrolyte of the sodium ion battery is injected into the liner tube 4 in the shell, and the diameter of the polyethylene/polypropylene microporous diaphragm is 10mm and the thickness of the polyethylene/polypropylene microporous diaphragm is 0.2mm in the embodiment, so that the volume V = pi x (10 mm/2) of the battery diaphragm 2 *0.2mm =15.7 μ L, and the addition amount of the electrolyte 15 is preferably: v' =1.8 × V =28.3 μ L, so that it sufficiently wets the battery separator 13 and wets the porous carbon electrode surface;
e. the sodium metal cathode is placed in the casing inside the liner tube 4, covering the battery diaphragm 13, and the electrolyte 15 is allowed to wet the surface of the sodium metal cathode, in this case the sodium metal cathode has a diameter of 10mm.
f. Sequentially placing a conductive pressing sheet 7, a conductive spring 6 and a conductive pressing column 5 into the lining tube 4 to form a conductive pressing mechanism, and pressing the conductive pressing sheet 7 on the metal sodium cathode;
g. the outer side of the shell 3 is connected with the inner side of the sealing sleeve 2 through threads and is screwed and sealed;
h. the outer side of the sealing sleeve 2 is connected with the inner side of the top cover 1 through threads and is screwed and sealed;
i. respectively connecting a working electrode post 8 and a reference electrode post 9 with threaded holes on the shell 3 and the top cover 1 through threads;
j. the connected battery device is horizontally placed on a sample table of an infrared spectrometer, a light source is aligned to a through hole in an observation window, and light rays pass through the observation window and are focused on the surface of a working electrode by adjusting the focal length of the light source;
k. and respectively connecting the working electrode post 8 and the reference electrode post 9 with corresponding electrode leads of an electrochemical testing device, setting relevant parameters, and acquiring electrochemical and in-situ infrared spectrum signals.
Example 3
Referring to fig. 1 to 5, the present embodiment provides a cell for in-situ spectroscopic analysis, which includes a top cover 1, a sealing sleeve 2, a housing 3, a liner tube 4 inside the housing, a conductive compression column 5, a conductive spring 6, a conductive compression sheet 7, a working electrode post 8, and a reference electrode post 9.
The bottom of the shell 3 is provided with a through hole 10 with the diameter of 2.8mm, the part of the through hole 10 outside the shell 3 is adhered with a regular hexagonal ultrathin beryllium piece with the side length of 4mm and the thickness of 400 mu m as a transparent sealing material 11 by a sealing glue, and the regular hexagonal ultrathin beryllium piece and the through hole 10 form an observation window together.
The material of the sealing sleeve 2 is polytetrafluoroethylene, the material of the liner tube 4 in the shell is polyimide, and the material of other components is metallic nickel.
The internal diameter of the top cover 1 and the external diameter of the sealing sleeve 2 are both 18mm, the internal diameter of the sealing sleeve 2 and the external diameter of the shell 3 are both 15mm, the internal diameter of the shell 3 and the external diameter of the lining tube 4 in the shell are both 14mm, and the internal diameter of the lining tube 4 in the shell and the external diameter of the conductive compression column 5 are both 13mm.
The inside of the cap 1, the inside and outside of the sealing sleeve 2, and the outside of the housing 3 are provided with threads so as to be connected to each other by means of a threaded engagement.
The conductive compression column 5 is provided with a cylindrical groove 5a with the depth of 8mm and the inner diameter of 8 mm; the length of the conductive spring 6 is 10mm, the outer diameter is 7.5mm, and the inner diameter is 6mm; the conductive pressing sheet 7 is provided with a cylindrical boss 7a with the length of 7mm and the diameter of 5.5mm, and after the conductive spring 6 is placed in the cylindrical groove 5a, the conductive spring and the cylindrical boss 7a of the conductive pressing sheet 7 can be sleeved to form a conductive pressing mechanism.
The top cover 1 and the shell 3 are respectively provided with a threaded hole which can be connected with the reference electrode post 9 and the working electrode post 8 in a threaded joint mode.
As shown in fig. 6, the above battery device is used, lithium cobaltate positive electrode is used as working electrode 12, polyethylene microporous diaphragm is used as diaphragm 13, graphite negative electrode is used as reference electrode 14, lithium ion battery electrolyte is used as electrolyte 15, the lithium ion battery is assembled, and the step of performing in-situ X-ray diffraction spectrum analysis on the working electrode is as follows:
a. inserting the inner liner 4 of the shell into the bottom of the shell 3;
b. sequentially placing a lithium cobaltate anode and a polyethylene microporous diaphragm into the liner tube 4 in the shell, so that the lithium cobaltate anode is opposite to the through hole 10; the diameters of the lithium cobaltate anode and the polyethylene microporous diaphragm are both 13mm, and the thickness of the diaphragm is 0.5mm.
c. Covering the other side of the through hole 10 with a regular hexagonal ultrathin beryllium sheet serving as a transparent sealing material 11, and tightly bonding the periphery of the regular hexagonal ultrathin beryllium sheet with the outer surface of the bottom of the shell 3 by using a sealant to form an observation window;
d. the electrolyte of the lithium ion battery is injected into the liner tube 4 in the shell, and the diameter of the polyethylene microporous diaphragm in the embodiment is 13mm, and the thickness of the polyethylene microporous diaphragm is 0.5mm, so that the volume V = pi x (13 mm/2) of the battery diaphragm 2 *0.5mm =66.3 μ L, the amount of the electrolyte 15 added is preferably: v' =0.7 × V =46.4 μ L, so that it sufficiently wets the battery separator 13 and wets the lithium cobaltate positive electrode surface;
e. the graphite cathode is placed in the casing inside the liner 4, covering the battery separator 13, and the electrolyte 15 is allowed to wet the surface of the graphite cathode, in this case 13mm in diameter.
f. Sequentially placing a conductive pressing sheet 7, a conductive spring 6 and a conductive pressing column 5 into the lining tube 4 to form a conductive pressing mechanism, and pressing the conductive pressing sheet 7 on the graphite cathode;
g. the outer side of the shell 3 is connected with the inner side of the sealing sleeve 2 through threads and is screwed and sealed;
h. connecting the outer side of the sealing sleeve 2 with the inner side of the top cover 1 through threads, and screwing and sealing;
i. respectively connecting a working electrode post 8 and a reference electrode post 9 with threaded holes on the shell 3 and the top cover 1 through threads;
j. the connected battery device is horizontally placed on a sample table of an X-ray diffraction spectrometer, a light source is aligned to a through hole in an observation window, and light rays pass through the observation window and are focused on the surface of a working electrode by adjusting the focal length of the light source;
k. and respectively connecting the working electrode pole 8 and the reference electrode pole 9 with corresponding electrode leads of an electrochemical testing device, and acquiring electrochemical and in-situ X-ray diffraction spectrum signals after setting relevant parameters.
The sequence of the above embodiments is only for convenience of description and does not represent the advantages and disadvantages of the embodiments.
Finally, it should be noted that: the above examples are only used to illustrate the technical solution of the present invention, and not to limit the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention.
Claims (10)
1. A cell for in situ spectroscopic analysis, comprising: the battery is characterized in that a shell lining pipe (4) is arranged in a shell (3), a conductive compaction structure is arranged in the shell lining pipe (4), a top cover (1) is arranged on the shell (3), and the shell (3) and the top cover (1) are sealed through a sealing sleeve (2);
a working electrode post (8) and a reference electrode post (9) are respectively fixed on the shell (3) and the top cover (1);
a through hole (10) is formed in the bottom of the shell (3), a transparent sealing material (11) covers the through hole (10) and is positioned on the outer side of the shell (3), and the through hole (10) and the transparent sealing material (11) form an observation window;
the conductive compression structure is formed by sequentially sleeving a conductive pressing sheet (7), a conductive spring (6) and a conductive pressing column (5).
2. The in situ spectroscopic cell of claim 1 wherein: a cylindrical groove (5 a) is formed in the bottom of the conductive pressing column (5), a cylindrical boss (7 a) is arranged on the top of the conductive pressing sheet (7), and the height of the cylindrical boss (7 a) is not larger than the depth of the cylindrical groove (5 a); the length of the conductive spring (6) is greater than the depth of the cylindrical groove (5 a), the outer diameter of the conductive spring (6) is smaller than the inner diameter of the cylindrical groove (5 a), and the inner diameter is greater than the outer diameter of the cylindrical boss (7 a); the conductive pressing sheet (7), the conductive spring (6) and the conductive pressing column (5) are sequentially sleeved to form the conductive pressing structure.
3. The in-situ spectroscopic cell of claim 1 or 2, wherein: the sealing sleeve (2) and the shell lining pipe (4) are made of insulating materials; the top cover (1), the shell (3), the conductive compression column (5), the conductive spring (6), the conductive pressing sheet (7), the working electrode pole (8) and the reference electrode pole (9) are all made of conductive materials.
4. The in situ spectroscopic cell of claim 1 or 2 wherein: the top cover (1), the sealing sleeve (2) and the shell (3) are matched through threads.
5. The in-situ spectroscopic cell of claim 1 or 2, wherein: the inner diameter of the top cover (1) is equal to the outer diameter of the sealing sleeve (2), the inner diameter of the sealing sleeve (2) is equal to the outer diameter of the shell (3), the inner diameter of the shell (3) is equal to the outer diameter of the shell lining pipe (4), and the inner diameter of the shell lining pipe (4) is equal to the outer diameter of the conductive compression column (5).
6. The in-situ spectroscopic cell of claim 1 or 2, wherein: the top cover (1) and the shell (3) are respectively provided with a threaded hole for fixing a reference electrode pole (9) and a working electrode pole (8) through threaded fit.
7. A method of using the in situ spectroscopic cell of any one of claims 1 to 6, comprising the steps of:
a. inserting the shell lining pipe (4) to the bottom of the shell (3);
b. sequentially placing a working electrode (12) and a battery diaphragm (13) into the shell lining pipe (4), and enabling the working electrode to be opposite to the through hole (10);
c. covering a transparent sealing material (11) on the through hole (10) from the outer side of the shell (3), and tightly bonding the periphery of the sealing material (11) and the outer surface of the bottom of the shell (3) by using a sealing agent to form an observation window;
d. injecting an electrolyte (15) into the liner tube (4) in the shell to fully soak the battery diaphragm (13) and wet the surface of the working electrode (12);
e. putting a reference electrode (14) into the shell lining tube (4), covering the reference electrode on a battery diaphragm (13), and enabling the electrolyte (13) to wet the surface of the reference electrode;
f. sequentially placing a conductive pressing sheet (7), a conductive spring (6) and a conductive pressing column (5) into the shell lining tube (4) to form a conductive pressing mechanism, and pressing the conductive pressing sheet (7) on the reference electrode (14);
g. the outer side of the shell (3) is connected with the inner side of the sealing sleeve (2) through threads and is screwed and sealed;
h. the outer side of the sealing sleeve (2) is connected with the inner side of the top cover (1) through threads and is screwed and sealed;
i. the working electrode post (8) and the reference electrode post (9) are respectively connected with the threaded holes on the shell (3) and the top cover (1) through threads;
j. the connected battery is placed on a sample table of a spectroscopy characterization instrument, a light source is aligned to a through hole (10) in an observation window, and light rays pass through the observation window and are focused on the surface of a working electrode by adjusting the focal length of the light source;
k. and respectively connecting the working electrode post (8) and the reference electrode post (9) with corresponding electrode leads of an electrochemical testing device, and acquiring electrochemical and spectral signals after setting relevant parameters.
8. Use according to claim 7, characterized in that: the spectroscopy characterization instrument is selected from a Raman spectrometer, an infrared spectrometer, an ultraviolet-visible spectrometer, a fluorescence spectrometer, an X-ray diffraction spectrometer or an X-ray photoelectron spectrometer; the electrochemical testing device is selected from an electrochemical workstation, a potentiostat or a battery charge-discharge testing system.
9. Use according to claim 7, characterized in that: the adding amount V 'of the electrolyte is determined according to the volume V of the battery diaphragm in the lining pipe of the shell, and V' = 0.5-2V.
10. Use of a cell for in situ spectroscopy according to claims 1 to 6 in situ spectroscopy, wherein: the in-situ spectroscopic analysis comprises in-situ Raman spectroscopic analysis, in-situ infrared spectroscopic analysis, in-situ ultraviolet-visible spectroscopic analysis, in-situ fluorescence spectroscopic analysis, in-situ X-ray diffraction spectroscopic analysis, and in-situ X-ray photoelectron spectroscopic analysis.
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